Synergistic pesticidal compositions containing carbamates and prosphates



United States Patent 3,193,452 SYNERGISTEC PESTICIDAL COMPOSITIONS CON-TAG CARBAMATES AND PROSPHATES Albert .liiger, Beriin-Hermsdorf, andHorst Peissker, Berlin-Charlottenhurg, Germany, assiguors to ScheringA.G., Berlin, Germany No Drawing. Filed Nov. 9, 1961, Ser. No. 151,167Claims priority, application Germany, Nov. 18, 1960, Sch 28,796; Feb.15, 1961, Sch 29,235, Sch 29,236 1 Claim. (Cl. 16722) This inventionrelates to pesticidal compositions, and more particularly to pesticidalcompositions containing two active agents which synergistically enhancethe pesticidal effects of each other.

Synergistic combinations of pesticidal agents have heretofore beenknown. Several known synergistic pesticide combinations have effectswhich are substantially greater than the sum of the effects availablefrom the individual constituents per se. An example of such asynergistic combination is a pesticide containing allethrin or pyrethrinin conjunction with piperonyl butoxide, methylenedioxyphenylacetal orthe n-octyl sulfoxide of isosafrol.

No method has heretofore been devised for predicting synergistic efiectsof pesticidal agents, particularly where their chemical structuregreatly differs. Even closely related compounds may differ in theirpesticidal effects in the presence of a third compound.

It has now been found that strong synergism exists between theconstituents of pesticidal compositions which include a carbamate of theformula In the above formulas, R R may be hydrogen or lower alkyl. R isa cyclic radical which may have a benzene, naphthalene, or pyrazolering. R, and R are lower alkyl. Y stands for a variety of radicals aswill presently become apparent, and X may be either oxygen or sulfur.

When employed jointly with the carbamates of Formula A very smallamounts of many phosphoric acid esters of Formula B show substantialsynergistic effects, although the same phosphoric acid esters do nothave any significant pesticidal effect when employed in the customaryamounts of 0.8 mg. per square decimeter of treated surface, and even at1.0 mg./dm.

The synergistic pesticidal mixtures of the invention may be employed assuch, or in combination with other pesticides such as insecticidal,acaricidal or fungicidal agents. Compositions may be formulated in aknown manner on the basis of the synergistic mixtures'of the inventionto suit the mode of application and the parasites to be affected.

The pesticidal compositions of the invention may thus include liquid orsolid carriers or diluents well known in themselves. Suitable liquidcarriers include water, mineral oil fractions, and solvents. Solidcarriers entirely compatible with the synergistic mixtures of theinvention include bentonite, fullers earth, gypsum, limestone,diatomaceous earth, pyrophyllite, silica, and talcum. Known surfaceactive agents and other adjuvants may be admixed in a mannerconventional per se. Such agents and adjuvants which are generallyuseful in conjunction with the pesticidal synergistic mixtures of theinvention include emulsifiers, wetting agents, binders, propellant3,193,452 Patented July 6, 1965 gases, perfumes, stabilizers attractingand repelling agents. The compositions resulting from combination of thesynergistic agents of the invention with carriers, adjuvants, and likesubstantially non-toxic materials may be in a state of comminution whichmakes them suitable for application by dusting or spreading. They may bepowdery mixes or granulated solids. Liquid compositions may be suitablefor application in jets, coarse sprays, or as fog-like dispersions. Theymay be incorporated in aerosol compositions and in fumigants.

The amounts of the synergistic mixtures which are suitable for use inthe protection of crop plants against acarids or mites and insects mayvary within wide limits. The quantities to be employed vary with theratio of the synergistic components in the mixture, with the method ofpreparing the pesticidal compositions, with the mode of application,with the desired result, and with the nature of the parasitescontrolled. The pesticidal composition may contain between approximately0.1 percent and percent of the individual active agents, and thesynergistic mixture may be employed successfully in concentrations aslow as 0.001 percent by weight. Generally, concentrations between 0.025percent and 10 percent of the synergistic mixtures in liquid or solidcarriers will be found most useful. Higher concentrations up to about 20percent by weight will be more advantageous only under exceptionalconditions.

The ratio of the components of the synergistic rnixtures may varybetween approximately 0.5 to 20 parts by weight of the phosphoric acidester of Formula B for each part of carbamate of Formula A. A ratio of 2to 10 parts phosphoric acid ester to one part carbamate is preferred.

The synergistic effects of the carbamates and phosphoric acid esters ofthe invention when employed jointly are evident from the followingillustrative examples. Comparative tests, the results of which arelisted in the tables, were performed under closely controlled uniformconditions. The results reported in Table I and II hereinfollowingconstitute averages of three series of tests.

EXAMPLE I TEST 0N HOUSE Fuss Carbamates and phosphoric acid esters weremechanically emulsified in water separately and jointly as shown inTable I. The emulsions were sprayed on glass plates and permitted todry, leaving a coating each square decimeter of which contained theamounts of active agents indicated in the table. The coated glass plateswere employed as covers on glass cylinders each of which contained 25house flies (Musca domestica L.) of a strain normally sensitive toinsecticides. The flies were three to four days old. After the periodindicated, the dead flies, damaged flies, and flies surviving withoutshowing symptoms of damage were counted, and the percentage efiiciencyof the agent or combination of agents in the coating was calculatedaccording to Abbotts formula.

The compounds employed in the tests on house flies are identified bycode designations as follows:

(A) Carbamates (A N-methyl- (3 -rnethyl-S-isopropylphenyl -carb amate CH3 C H3NHCO O 0 5113 C H: (C Hz) 2 (AN-methyl-(3-methyl-6-isopropylphenyl)-carbamate (AN-methyl-phenylcarbamate (A N-methyl-u-napthylcarbamate (A N-dimethyl-3-methyl-5 -isopropylpyrazoly1) -carbamate r phoric acid (B O,C'-diethylester of N-diethylamido-thionophosphoric acid 3 F 7 02HF0\ z s) a CzHr OS (B5) 0,0f-diethyl ester of N-cyclohexylamido-thionophosphoric acid (BN- (0,0'-diethyl-thionoph0sphoryl) -morp'holine cans-o 0 (B N-(0,0'-diethyl-thionophosphoryl-piperi dine 7 (B 0,0'-diethyl ester ofN-camphyl-amidothionphos- V (B O,O- diethyl ester ofN-cyclohexylamidophosphoric acid Nn-clnn TABLE I Percent effieiencyafter 24' hours 7 Dosage of active compound(s) in Active compounds a 4EXAMPLE II TESTS 0N GRANARY WEEVILS Carbamates and phosphoric acidesters in aqueous 1 emulsions were applied to the lower halves of Petridishes in the same manner as in Example 1. After the coating had dried,100 to 120 granary weevils (Calandra granaria L.) were placed in eachopen dish. The weevils that had died, were lying on their backs, showedsymptoms of damage, and survivors without noticeable symptoms werecountedpand the percentage efiiciency of the tested coatings wasdetermined according to Abbotts formula.

In addition to compounds identified in Example I, the followingcarbamates'and phosphoric acid ester amides were employed in the teststhe results of which appear in Table II.

(B) Phosphoric acid ester amides (B 0,0-diethyl ester ofN-4-methylphenyl amidophosphoric acid (MILK-'0 NH- CH3 7 Q I V C H O \O(B 0,0'-diethyl ester of N-ethylamidophosphoric acid 02115; O N H C2115s. r CzH50 O V (B N- (0,0'-diethylphosphory1) -morpholine r t 02115-0 POHFCHQ' 2115-0 0 B N- 0,0'-diethylphosphory1) -piperidine our-0H2 C H-O\ /N\ /CH;;

' /P\ on; CH 7 CzHzr-O O 7 TABLE II V Dosage of Percent Active compoundsactive comefliciency pound(s) in after 24 mgJdm. hours EXAMPLE III Tasrs ONVVIIOUSE FLIES' Thetests the results of which are listed in TableIII were performed, in the same manner as in Example I. The

coatings produced contained 0.02 mg./dm. of the carbamate A and amountsofa thionophosphoric acid indicated as a multiple of the amount of ANone of the thionophosphoric acid esters identified hereinbelow as B 50013 had any effect on house flies when applied singly (B)Thz'onophosphoric acid esters (B) T hionophosphoric acidesters-Continued B H 13) C2 %S OH: (B27) 01130 S JJH=(CH3)3 (B28) 1130CH3 (B 11) C2H5- 0 S C 2H5 O S \P% CH3 \P% CH CH3 CzH -O O C H O \O(OHQFOH (B19) o11110 s OH (B) 011150 s CH 15 /P a a /P\ z sO 0- CzHaO 0-C1 (CH1)1OH CH(CH3 z (Ban) CgH O\ /S OH (B10) CH3O\ /S OH 20 /P a 91 11(1311mm)! (B11) c1H50 s CH (B17) 01130 S CH 1 3 a a. V /P\ CzHsO O N OCHaO O- CH(OH3)2 (CH3)2CH TABLE III (B1B) a S P CH3ThlonophosphorlcacldesterBemployethomt-' Ratio Percentage 3 5 1y with0.02 mgjdm. of compound A1 A1213 efficiency 01130 0-- 01 after 24 hoursCH3 gim 1:0 36.6 .1 1:1 0.0 (B111) CzHsO\ S CH3 1E2 P 40 88 7 OZHN/ 1:294.4 1:5 100.0 3.1 1:1 91.8 We 12% 12:1 (B20) OHGO s CH B 13%.8

7 2 I B 11 322 CH O 0 l 122 10010 11 1111 (011931 BM 3 :3 (B21) 01130 S13 121 7919 \P CH 13 i i 32'? 3 no 2 B 1:1 88.4 01130 o- 6 0111, 1 3.(B11) 011150 s B i 8 E 1 R M 122 10010 0 11 0 O-- C (C Hz) a B1,, g

: 1 B CH 0 B: 1:1 75.0 23) a H: 1:1 87.2 P 1 B 21-2 'm 2 cnao oc cna a B1=5 80.1

/P\ EXAMPLE IV C H 0 O C CH 2 5 Q V Tnsrs 0N GRANARY WEEVILS (B OH O s a25 3 The compounds tested 1n Example III on house flies P were tested ongranary weevils by the technique described 01110 O O( Ha)a n1 Exam 1eII. The results obtarned on granary weevrls P I I I are shown 1n TableIV 1n which the compounds employed (B16) 011150 3 are identified by thecode designations used in the preced- 111g examples. 0.8 mg./d1n. of theseveral thronophos- P phoric acid esters were without effect on theweevils when 0,1150 0- H employed slngly.

Percentage eflieiency after hours TABLE VI EXAMPLE v1 TESTS ON GRANARYWEEVILS I Results obtained on granary weevils'by'the technique ofExample II with additional synergistic mixtures of the inabsence, of acarbamate of the invention in amounts up to 1 mg./dm.

were without effect on granary weevils when used in the 1 EXAMPLE VIITESTS on HOUSE "FLIES Tests by the technique of Example I were performedon house fiies in a series of experiments in which 0.16

nag/rim. of carbamate A were combined with phosphoric acid ester-s inthe ratios indicated in Table VII.

The phosphoric acid esters listed in Table VII when tested in theabsence-of a carbamate had no measurable eifect on house flies inamounts up to 0.8'mg./dm. with the cXcBptlOIl of compounds B and B forWhich the lower limit of efiiciency was respectively somewhat above 0.1and 0.04 mg./dm.

7 TABLE IV 0 l l lll lllllllll i h RA e n .m n

m 7 ed, ym 7O 1 m m B V MM 1 m2 mm r m OI. ave m mm m m0 m I i n 0 MW. en m mu m m rvv mun M Mm T NB B B B B B BBBBBB B BB BBB EXAMPLE V TESTSON House FLIBs Additional combinations of carbarnatesandthionophosphoric acid esters were tested on house'fiies by thetechnique of Example I. i Table'V lists the results achieved.

Code designations A2, A4, A5, B18 and B25 refer o The followingcompounds not "identified in the previously identified compounds Thefphosphoric acid Qedlng eXampleS are listed 11 Ta l VII: derivatives hadno effects on house flies when employed in amounts far in excess of thatused in the tests reported on in Table V.

(B 0,0'-diethyl-O"-4-tert-amylphenyl thionophosphate elm-o s T r I \1/C2H5-'0/ \Q .CsHu

(B 0,0-diethyl-O-4-isovalerylphenyl thionophosphate (B0,0'-diethyl-O"-4-isoheptylphenyl thionophosphate (B 0,0'-diethy1-O"-4-(3-oXorbutyl-1)-phenyl thionophosphate i (B )0,0 diethylo"-phenylphosphate (B 0,0'-diethyl-O '-(3-1nethyl-S-isopropylphenyl)phosphate p (B 0,0-diethy1-O"-(3-methyl-4-isopropylphenyl) phosphate 7(B 0,0-diethyl-0-4-tert-butylphenyl phosphate (BO,O-diethyl.-O"(3-methyl-6-isopropylphenyl) .phosphate y (B0,0'-diethyl-O"-3-rnethy1phenyl phosphate (B0,0'-diethyl-S-phenyl-thiolophosphate 24 hours C3Hfl-0 8-0011! (B0.0'-diethyl-S-phenyl clithiophosphate CzHs-O 5 0 00 0 350 0 00 700018SE0 0 111 a 1 1 CH (C a) 2 7 Ratio TABLE V Dosage of A compound ingJdru.

In addition to previously identified compounds Table V includes resultsobtained with the tel-lowing compounds:

Active compound(s) TABLE VII Percentage efficiency after 24 hoursEXAMPLE VIII TEST ON GRANARY WEEVILS Employing the technique of ExampleII, the synergistic combinations of pesticidal agents tested againsthouse flies in Example VII were used against granary weevils. In thesetests, the amount of carbamate compound A was 0.02 mg./dm. Thephosphoric acid ester derivatives listed in Table VIII were entirelyineffective against granary weevils up to amounts of 0.8 mg./dm. withthe exception of compounds B and B for which the lower limits ofefliciency were found to be above 0.1 and 0.05 1ng./dm. respectively.

EXAMPLE IX TEST N House Funs Several of the phosphoric acid esterderivatives of Examples VII were tested in conjunction with additionalcarbamate derivatives in their effects on house flies. The technique ofExample I was employed. It will be noted that the phosphoric acid esterderivatives listed in Table IX have no measurable eflect on house fliesin the amounts employed in conjunction with carbamate derivatives.

TABLE IX Dosage of Percentage eificieney Active c0mp01md(s) A-eompoundRatio after mg./dm. A: B

2 Hours 24 Hours While the invention has been described with particularreference to specific embodiments, it is to be understood that it is notlimited thereto, but is to be construedbroadly and restricted solely bythe scope of the appended claim.

We claim:

A pesticidal composition containing as active agent a mixture of (a) acarbamate selected from the group consisting of:

N-methyl-(3-methyl-S-isopropylphenyl)-carbamate N-methyl(3-methyl-6-isopropy1phenyl)-carbamate N-methyl-phenyl-carbamateN-methyl-a-naphthyl-carbamate N-dimethyl- 3-methyl-S-isopropylpyrazolyl)-carbamate 3-methyl-S-isopropylphenyl-carbamate N-methyl- (3-methyl-4-isopropylphenyl) -carbamate; and (b) a phosphoric acid esterselected from the group consisting of:

0,0-diethyl-N-ethylamidothionophosphate0,0'-diethyl-N-camphylamidothionophosphate0,0'-diethyl-N-cyclo-octylamidothionophosphate0,0-diethyl-N-diethylamidothionophosphate0,0-diethyl-N-cyclohexylamidothionophosphate N-0,0'-diethyl-thionophosphoryl) -morpholine N- (0,0'-diethyl-thionophosphoryl -piperidine0,0'-diethyl-N-cyclohexylamidophosphate0,0-diethyl-N-4-methylphenylamidophosphate0,0-diethyl-N-ethylamidophosphate N-(0,0'-diethylphosphoryl)-morpholineN- 0,0'diethylphosphoryl) -piperidine0,0-diethyl-O"-(3-methyl-5-isopropylphenyl)-thionophosphate0,0'-diethyl-O"-(3-methyl-5-isopropyl-4-chlorophenylthionophosphate0,0-dimethyl-O"- 3-methyl-S-isopropylphenyl thionophosphate0,0'-dimethyl-O"-(3-methyl-5-isopropyl-4-chlorophenyl) -thiono phosphate0,0- diethyl-O"- (3 -methyl-6-tert.butylphenyl) -thionophosphate0,0-dimethyl-O' 3-methyl-6-tert.butylphenyl) thionophosphate0,0-dimethyl-O (Z-methyl-4-tert.butylphenyl) thionophosphate0,0-diethyl-O"-4-tert.butylphenyl-thionophosphate0,0'-dimethyl-O"-4-tert.butylphenyl-thionophosphate0,0-dimethyl-O"-4-tert.butylphenyl-thionophosphate0,0'-diethyl-O-(3-methyl-S-isopropylphenyl)-phosphate0,0'-diethyl-S-phenyl-thi0lophosphate0,0'-diethyl-S-phenyl-dithiophosphate; and a carrier therefor; the totalconcentration of said mixture being between about 0.025% and about 10%by weight of said composition; the ratio of the phosphoric acid ester tothe carbamate being between about 2:1 and about 10:1 parts by weight.

References Cited by the Examiner UNITED STATES PATENTS 2,945,780 7/60Jones 167-30 2,990,317 6/61 Jones 167- 22 2,990,319 6/61 Jones 167-22OTHER REFERENCES Frear: Chemistry of the Pesticides, 3rd edition (1955),pages 79, 82 and 83.

LEWIS GOTTS, Primary Examiner.

MORRIS O. WOLK, Examiner.

